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A new monomer for application in the gelcasting process has been designed and synthesized, following the green chemistry
trend to use non toxic and renewable compounds. Xylitol was the main substrate for the synthesis that included 3 stages. The
final product, named 1-O-acryloylxylitol, was tested regarding its effectiveness as the processing agent for fabrication of
alumina elements by gelcasting method. Rheological properties of the ceramic slurries were studied as well as the properties
of shaped elements before and after sintering. The results are compared to those obtained by applying commercial monomer
2-hydroxyethyl acrylate.
Keywords: alumina, gelcasting, low-toxic monomers, xylitol
Podążając za trendem „zielonej chemii”, zakładającym m.in. wykorzystywanie nietoksycznych i odnawialnych surowców
w technologii, zaprojektowano i zsyntezowano nowy monomer przeznaczony do zastosowania w procesie odlewania żelowego.
Wyjściowym substratem trójetapowej syntezy był ksylitol, a finalnym produktem 1-O-akryloiloksylitol. Otrzymana pochodna
została sprawdzona pod względem efektywności polimeryzacji in situ w ceramicznej masie lejnej na bazie tlenku glinu. Zbadano
jej wpływ na właściwości reologiczne stosowanych zawiesin. Odlano serie kształtek, dla których wyznaczono podstawowe
parametry w stanie surowym oraz po spiekaniu. Wyniki porównano stosując równolegle komercyjnie dostępny monomer
akrylan 2-hydroksyetylu.
cussed and the main results concerning the properties of the mean particle size D50 = 0.15 µm and specific surface area
suspensions and gelcast elements are compared to those ob- SBET = 14.5 m2 /g. Diammonium hydrocitrate, DAC (POCh,
tained with the application of commercial low-toxic monomer Poland) and citric acid, CA (Sigma) were used as disper-
2-hydroksyethyl acrylate. sants. N,N,N’,N’-tetramethylethylene-diamine, TEMED (Flu-
ka) played the role of activator and ammonium persulfate,
AP (Aldrich) used in the form of 1wt % aqueous solution,
2. Experimental was the initiator of polymerization. Two monomers were
2.1. The synthesis of the new compound applied, newly synthesised Akr-X and commercially avail-
able 2-hydroksyethyl acrylate, HEA (Fluka) accompanied with
The synthesis route of 1-O-acyrloylxylitol (Akr-X) is a cross-linking agent, N,N’-methylenebisacrylamide, MBAM
shown in Fig. 1. The aim of the synthesis, was the selective (Fluka). The molecules of that gelating system is shown in
substitution of acryloyl group instead of hydroxyl group to the Fig. 2.
xylitol molecule. It was carried out in three stages, analogous
to the synthesis route reported for 3-O-acryloyl-D-glucose [5].
In the first stage (Fig. 1a) was aimed at blocking four from the
five hydroxyl groups in xylitol molecule by the reaction with
acetone in acidic medium. The second stage was the esterifi-
cation of the only remaining hydroxyl group, done by acryloyl Fig. 2. Chemical formula of a) 2-hydroxyethyl acrylate (HEA) and
chloride in the presence of amine. It allows to introduce the b) N,N’-methylenebisacrylamide (MBAM)
functional group with the double bond to the molecule. The
third stage (Fig. 1c) was focused on acidic hydrolysis that
unlocks the hydroxyl groups. The final product is ready to 2.3. Shaping procedure
use as an aqueous solution (20%) or as a pure monomer after
evaporating the solvent. Firstly, ceramic slurries were prepared at room tempera-
ture in the containers made of alumina. The dispersants, the
monomer and activator were dissolved in distilled water and
the ceramic powder was added at last. The contents of all
additives are listed in Table 1. The slurries were mixed in
a planetary ball mill (PM100, Retch) for 60 minutes with
a speed of 300 rpm. Next, the slurries were degassed un-
der reduced pressure in a vacuum desiccator supplied with a
magnetic stirrer. Just before casting the slurries into the round
plastic moulds (ϕ20), the initiator was added and they were
mixed for 3 minutes by magnetic stirrer. The access of the
fresh air was cut off by placing the mould filled with slurries
under cover for 6h to complete the gelation process. After the
gelled bodies were obtained and removed from the moulds
they were dried in air at room temperature for 24h, then at
Fig. 1. The synthesis of 1-O-acryloylxylitol (Akr-X)
50◦ C for 24h. Just before sintering they were dried at 105◦ C
for 1h. The specimens were sintered at 1500◦ C for 2h.
2.2. Materials and other components of the slurries
TABLE 1
The composition of the ceramic suspensions prepared for the gelcasting
2.4. Characterization techniques The monomer content in the suspension is a crucial issue,
because after the polymerization, that macromolecular net-
The viscosities of the suspensions after mixing and de- work is responsible for the mechanical strength of the green
gassing, but before initializing of the polymerization, were elements. Generally, the larger the network is, the stronger the
measured by using Brookfield DV+II- Pro rheometer (Brook- green bodies, so higher content of the monomer in the sus-
field Engineering Laboratories Inc. Massachusetts, USA) as pension leads to higher mechanical strength of the specimens
a function of shear rate. The idle time was calculated on the before the sintering. However, the more organic substances
basis of viscosity measurements in time at a constant shear are added to the suspension, the more difficult it is to burn
rate 0.1s−1 , 3 minutes after addition of the initiator to the sus- them out during sintering, so the easier it is to cause any
pension. The densities of green and sintered specimens were defects. Usually the amount of the monomer in the gelcasting
measured by the Archimedes’ method in kerosene. The tensile procedure should be not larger that 5wt % and the amount of
strength of the green bodies was determined by the ‘Brazilian 3wt % is thought to be the minimum quantity.
test’, so that a circular disk was placed between two platens and
compressed producing a nearly uniform tensile stress distrib- 3.2. The idle time control
ution normal to the loaded (vertical) diametral plane, leading
to the failure of the disk by splitting. The tensile strength was
calculated as σt = (2P/πTD), where P is force, and T and D are The composition of activator (catalyst) and initiator is
the thickness and diameter of the disk [9]. The microstructure essential additive to start the polymerization in situ in the
of the specimens was observed in scanning electron micro- ceramic suspension. Their contents also allow to control the
scope ZEISS (Germany). idle time of the process, it means the time interval between
adding the initiator to the suspension and the real start of the
reaction. The creation of the polymer leads to the rapid and
3. Results and discussion big increase of the viscosity of the slurries. From the tech-
nological point of view, the idle time shouldn’t be then too
3.1. Influence of the monomers on viscosity of the quick, as all the operations concerning mixing and filling the
slurries suspension to the mould regard some time. However, the idle
time shouldn’t be too long, because of the simple economi-
As shown in Fig. 3., all of the viscosity curves reveal cal issues – the whole shaping process should be as fast as
the shear-thinning behavior of the suspensions. All of the sus- possible. At the same time, the initiator content has a large
pensions present low viscosity, low enough to fill the complex influence on the mechanical properties of the green bodies.
moulds in details, even despite very high alumina content (over The mechanism of polymerization assumes creating free radi-
50vol %). However some differences are visible. The amount cals and chain reaction. Too high initiator content leads to the
of dispersants were matched individually for the slurries with creation of too many free radicals that start the polymerization
different monomers, on the basis of viscosity curves obtained and finally a lot of short polymeric chains are created. On the
for the suspensions where 3wt % of monomers were applied. other hand, too low initiator content might be not efficient.
Both monomers have a positive impact on the viscosity. 5wt % The ideal situation is when only few long polymeric chains
addition of each monomer decreases the viscosity, that is lower are created.
than the viscosity of the slurry with 3wt % monomer content. For gelcasting the elements for that research, the poly-
Moreover, the viscosities of the suspensions with HEA are merization was initialized by 0.3 and 0.1 wt % of APS for the
lower than with Akr-X, even despite the higher solid content. slurries with Akr-X and HEA respectively, having the idle
That was to be expected, because HEA is a low-viscous liquid time around 25 minutes. Table 2 lists the values of the idle
whereas Akr-X is a high-viscous resinous substance. time for different amount of initiator.
TABLE 2
The idle time values controlled by the initiator content
Akr-X 2 0.5 20
2 0.7 18
2 1.0 14
2 0.1 23
HEA 2 0.3 9
2 0.5 6
Fig. 3. Viscosity curves for alumina suspensions with HEA and
2 1.0 4
Akr-X (compositions according to Table 1)
1302
obtained by gelcasting a suspension with Akr-X are charac- [2] A.C. Y o u n g, O.O. O m a t e t e, M.A. J a n n e y, P.A.
terised by very high values of tensile strength of green bod- M e n c h h o f e r, J. Am. Ceram. Soc. 74, 612 (1991).
ies, as well as very high densities of sintered elements. The [3] J. Y a n g, J. Y u, Y. H u a n g, J. Eur. Ceram. Soc. 31, 2569
quality of the products is incomparably better than if com- (2011).
mercial 2-hydroxyethyl acrylate (HEA) together with MBAM [4] P. B e d n a r e k, Y. S a k k a, M. S z a f r a n, T. M i z e r s -
k i, J. Eur. Ceram. Soc. 30, 1795 (2010).
as cross-linking agent is applied for the same procedure. The
[5] P. F a l k o w s k i, P. B e d n a r e k, A. D a n e l s k a,
research shows that not only acryloyl derivatives of monosac- T. M i z e r s k i, M. S z a f r a n, J. Eur. Ceram. Soc. 30, 2805
charides, but generally of polyhydroxycompunds are promis- (2010).
ing group of substances to use in the process. [6] M. S z a f r a n, P. B e d n a r e k, A. S z u d a r s k a, Ad-
vances in Science and Technology 62, 163 (2010).
Acknowledgements [7] A. S z u d a r s k a, T. M i z e r s k i, M. S z a f r a n, Archives
of Metallurgy and Materials 56, 1211 (2011).
This work was partially supported by the Ministry of Science [8] C. T a l l o n, D. J a c h, R. M o r e n o, M.I. N i e t o, G. R o -
and Higher Education of Poland (Grant No. N N209 19 97 38). k i c k i, M. S z a f r a n, J. Am. Ceram. Soc. 90, 1386 (2007).
[9] J.R. C a p u a P r o v e t i, G. M i c h o t, Int J Fract. 139, 455
(2006).
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